Striker compositions



No Drawing. Filed Oct. 31, 1966, Ser. No. 590,483 Int. Cl. COM 3/ 08 US.Cl. 149-49 Unite 10 Claims ABSTRACT OF THE DISCLOSURE Waterproofmatch-striker compositions and manufacturing processes therefor aredisclosed. These compositions have increased pot-life at elevatedtemperatures and comprise as the binder therefor: (A) a proteinaceousadhesive material and (B) a hydrolyzed interpolymer of an alkyl vinylether and maleic anhydride which are cross-linked in situ to awater-insoluble state, preferably in the presence of an accelerator, atelevated temperatures.

This invention relates to match striker compositions in general and,more particularly, to novel water-proof match-striker compositions, toprocesses for their production and to methods for their application inthe match industry.

The common variety of safety matches which are sold either in boxes orin cardboard folders must be struck against a friction element in orderto initiate the burning process which elements are usually referred toas striker compositions. Compositions for the formation of matchstrikers form an essential part of the safety match industry, andintense efforts have been extended to provide satisfactory strikersurfaces.

In general, safety match production and use comprise two basiccomponents:

(1) a striking friction surface containing a readily ignitable compound,and

(2) a pyrotechnic match which is capable of ignition. The strikerassembly generally comprises an igniting agent, a friction agent, and abinder material to cement the friction agent or abrasive and theigniting agent into a coherent mass and to adhere this mass to a basesubstrate, such as a cardboard or wooden matchbox. The pyrotechnic matchusually comprises a paper or wood sliver, the tip of which is coatedwith a composition containing a material which can yield free oxygen tosupport combustion, such as potassium chlorate, readily combustiblefillers, such as rosin or sulfur, inert fillers for body, a binder and acolloidal agent.

Heretofore, the compositions employed in forming the match-strikersurfaces have been characterized by the lack of resistance to water,non-uniformity in the striking surface, poor pot-life of the compositionand poor sensitivity to the action of the match in achieving the desiredaims. Various attempts, however, have been made to overcome theseseveral previous disadvantages and enhance the scope of the commercialapplications available to the match-striker composition. In the main,these prior attempts have involved the use of various types of binderingredients, such as synthetic materials of various types, thewater-proofing of the compositions by various methods and the use ofsundry physical manipulations of the binder compositions in order toovercome the several disadvantages enumerated hereinabove. However, noneof these prior methods and materials have operated to produce asatisfactory striker composition, especially as to the problemsinvolving water resistance and stability.

Of the several binders which have been employed in these match-strikercompositions heretofore, there may be mentioned such materials ascasein, synthetic mateatent O 3,441,456 Patented Apr. 29, 1969 rials andmaterials derived from proteinaceous origin, such as animal glue, pitchglue and the like. Casein, for example, has not been satisfactory as abinder as this material tends to gel on standing and, in addition, has astrong tendency to putrefy when employed as a striker compositionbinder. Also, the films formed from casein bases are not generallyconsidered sufiiciently water resistant, a factor which is of the utmostpriority in achieving a satisfactory match-striker composition.Moreover, much of the casein used in the United States match industrymust be imported and, therefore, is subject to wide fluctuation inmarket price.

As mentioned, various synthetic lattices have also been suggested asbinders, such as polystyrene, for example. However, the lattices ofthese materials are similarly not truly water resistant, particularlywhen the coatings containing these materials are subjected to long-termimmersion in water.

A particularly desirable binder for use in match-striker compositionswould be materials formed from a proteinaceous origin, such as animalglues and fish glues and the like, as these materials are economical andreadily available. However, these materials have been found to beparticularly poor in their resistance to water and, thus, are easilysolubilized when contacted with an aqueuos environment. Moreover, thelack of uniformity as to quality is a characteristic of the availablesupply of these proteinaceous materials because of the natural origin ofthe material and their ready susceptibility to bacterial attack under avariety of conditions. The first-mentioned drawback, namely, lack ofwater resistance, has proven particularly objectionable since thisreduces considerably the scope of commercial applications available forthis type of match-striker composition material.

Various procedures have been resorted to heretofore in an effort toovercome or otherwise mitigate this poor resistance to watersolubilization and thereby render materials of protein originsatisfactory binders in the formation of match-striker composition. Inthe main these procedures 'have involved primarily the utilization of aninsolubilization or tanning" technique whereby the protein material isconverted to a substantially water-resistant form. Insolubilization ofthe protein material has heretofore been attempted, for example, by theuse of one or more tanning agents as formaldehyde, substances whichyield formaldehyde under the conditions of the tanning treatment, chromealum, bichromate, ferric salts, and the like. Of the materialsmentioned, perhaps formaldehyde has thus far proven to be the mosteffective from a commercial standpoint since its use does not impartspurious coloration to the glue product. However, tanning processesbased on the use of formaldehyde are not without one or more attendantdisadvantages. For example, the addition of formaldehyde to the gluesolution is accompanied by an almost instantaneous insolubilizationreaction with the result that substantial immobilization of the glueproduct occurs thereby presenting serious obstacles for handling of theinsolubilized glue product. Furthermore, it has been found that the glueproduct so immobilized cannot be satisfactorily coated onto theparticular substrate, in this case, the base to which the match-strikercomposition is to be applied. Moreover, when the protein material istanned or hardened such compositions tend to be softened when wet bywater and thus will not generate the adequate friction required for theignition of matches. A further and probably more important disadvantageoccurring with the employment of tanning procedures with formaldehyde orformaldehyde donors is that there is thus created noxious fumes duringprocessing, and, hence, the commercial aspects of such a product wouldbe considerably retarded.

A still further disadvantage of a glue-based striker compositioninsolubilized by the use of tanning procedures now known to the art isthat it shortens the pot-life of the composition and thus renders itpractically inoperative for use in match-striker compositions.

Various other techniques have also been attempted in order to place abinder of protein origin in a state whereby it may be usedsatisfactorily as a match-striker binder composition. One of thesetechniques has been by the use of hot melt application. By thistechnique, the binder is coated on the substrate and, while still hot,is powdered with the abrasive material to be included in the strikercomposition. However, this method requires removal of the excessabrasive which did not stick to the, binder and thus an untidy extraprocessing step is generally necessary. Another technique which has beensuggested for water proofing the striker composition is by theapplication of a water-resistant overlay to the striker film. However,these coatings are often impaired after repeated strikings with matchesand thus form sites which are readily penetrated by water. Moreover,this second coat is obviously an extra operation and will serve to addprocessing costs and thereby increase ultimate costs of the strikerproduct.

It is accordingly one object of this invention to provide novelmatch-striker compositions employing a novel binder in formation of thecompositions.

It is a further object of this invention to provide novel match-strikercompositions which are water-proof, have excellent pot-life, andotherwise mitigate the disadvantages attendant to striker compositionsof the prior art.

A still further object of this invention is to provide novel,water-resistant match-striker compositions, methods for preparing thesame and their application, wherein a novel binder of protein origin isemployed.

A still further object of the invention is to provide novelwater-resistant match-striker compositions having increased pot-life atelevated temperatures which utilize adhesive binder compositions ofproteinaceous origin and methods for preparing the same, as well asprocesses for their application in the match industry.

Other objects and advantages of the present invention will becomeapparent as the description thereof proceeds.

In accordance with this invention and in satisfaction of the foregoingobjects and advantages, there are provided in its broader aspects novelmatchstriker compositions comprising an igniting agent, a frictionagent, and a binder material to cement the igniting agent and frictionagents into a coherent mass, the binder material comprising: (1) aproteinaceous adhesive material, and (Q) a hydrolyzed interpolymer of analkyl vinyl ether and maleic anhydride. In addition, there may also beincluded within the binder composition, an accelerator material whichaids in insolubilization of the porteinaceous material.

According to this invention, it has been found that use of the novelbinder composition of this invention permits the use of an economicalreadily available binder, namely, a glue material, without the need fornoxious tanning agents and Without the'undesirable limited pot-life ofglue-formaldehyde compositions such as are ordinarily employed ininsolubil-izing adhesives of protein origin. Moreover, the utilizationof the binder compositions of this invention permits the use oflow-grade, inexpensive glues, particularly those of low gel strength, byupgrading them through cross-linking action with the hydrolyzedinterpolymers of alkyl vinyl ethers and maleic anhydrides. Under theconditions employed in forming these binder compositions, theinterpolymer serves to insolubilize the proteinaceous material andthereby renders the mixture particularly suitable in match-strikercompositions.

The striker compositions formed employing the novel binders describedhereinbelow, which are obtained from proteinaceous materials, have beenfound to exhibit the excellent high water resistance of strikermaterials which referred to herein,

are based on glues formed by conventional tanning procedures. However,the insolubilization of the glues employed herein by the use ofhydrolyzed interpolymers of alkyl vinyl ethers and maleic anhydride havebeen found to eliminate the tendencies for the glue to putrefy and thusovercomes one of the primary disadvantages of the glue compositionsemployed heretofore.

In general, the novel striker compositions of this invention are formedby intimately admixing an aqueous solution of the proteinaceousadhesive, an aqueous solution of the hydrolyzed interpolymer of an alkylvinyl ether and maleic anhydride and optionally an insolubilization accelerator at temperatures ranging from about room temperature toelevated temperatures on the order of the liquifaction point of theproteinaceous adhesive and then adding thereto the igniting agent andthe friction agent. A convenient method for the addition of the ignitingagent and the friction agent is by the use of an aqueous slurry.Thickeners and inert fillers can be added as desired to achieve therequired consistency.

The proteinaceous adhesives which are employed in formation of the novelbinders of this invention are of proteinaceous origin and are commonlydescribed as animal glues, fish glues, and the like. The various glues,as are generally described as organic colloids of protein derivation.They are generally obtained by boiling animal matter, such as skin andbone, in water and then drying the extract. Chemically, these materialsare known as polypeptide chains terminated at one end of the molecule byan amino group and at the other end by a carboxyl group. A pure form ofproteinaceous material which has been found to be particularly suitablein the process of this invention is gelatin.

Any grade of animal glue and/ or fish glue may be employed to advantagein the present invention, the only requirements with respect theretobeing that they conform to the usual commercial standards as regardsquality, purity, and the like. Any of the glue materials commonlyemployed in the production of animal and/or fish glue adhesives arequite satisfactory. The animal or fish glue is employed in the form ofan aqueous solution which can be readily prepared by stirring the gluein question into cold water preferably containing a preservative, untilthoroughly wet-out and allowing the resultant slurry to swell. Theslurry is then heated to a temperature of from to F. during which timethe mixture is maintained under agitation. In this manner, solution ofthe glue is readily achieved.

The vinyl alkyl ether/maleic anhydride interpolymers which are found tobe eminently suitable for use in producing the hydrolysates utilizableto advantage in the present invention are readily availablecommercially. Particularly good results are obtained with productsavailable under the trade name designation Gantrez-an sold by theGeneral Aniline & Film Corporation. These products are water soluble,linear, resinous interpolymers of methyl vinyl ether and maleicanhydride having molecular weights ranging from about 156,000 to about4,000,000.

Structurally, these interpolymers can be represented by the followingformula:

wherein n has a value of from about 1,000 to about 25,000. Accordingly,such products are usually designated in terms of specific viscosity,this being considered a more accurate indicia for polymeridentification. Thus, expressed in terms of specific viscosity, theproducts encompassed by the above formula possess an nsp value asmeasured at a one gram concentration in methyl ethyl ketone at 25 C.within the range of from about 0.1 to about 3.5, with a range of 1.5 to3.5 being preferred.

Hydrolysis of the foregoing polymeric materials can be readilyaccomplished by merely adding the interpolymer to an aqueous medium andallowing the solution thus obtained to stand from approximately 24 to 48hours in a closed container at room temperature. Occasional stirring canbe employed if desired. The hydrolysis reaction can be accelerated byemploying elevated temperatures on the order of 90l00 C., withtemperatures of 95-99 C. being preferred.

In carrying out the hydrolysis reaction, the aqueous medium ispreferably pro-heated to the previously indicated temperature range andmaintained under stirring sufficient to produce a rapidly whirlingvortex. The interpolymer is then introduced directly into the vortex inorder to expedite polymer Wet-out and dispersion. Stirring is maintainedunder the elevated temperature conditions 'until complete solution ofthe interpolymer material iS achieved, during which time the slurryexhibits an increase in viscosity. Completion of the polymer dissolutionis indicated by a decrease in solution viscosity and by an almostinstantaneous change in appearance from milky white to transparent.Since the adhesive compositions modified in accordance with the presentinvention are in most instances provided in aqueous media, it will bereadily understood that hydrolysis of the interpolymer may be carriedout either in the presence or absence of the adhesive substance, e.g.,animal glue. The former, which can be termed for convenience an in situhydrolysis is, however, a less preferred method for carrying out thehydrolysis reaction, since in many instances, it can result in asignificant shortening in the pot-life of the glue composition.

In explanation of the foregoing, it has been postulated that, ifhydrolysis is effected in the glue solution at room temperature, theseveral days time required for all anhydride rings to open wouldcorrespondingly reduce pot-life. This conclusion is borne out inexperimental data and observations which establish that insolubilizationof the glue composition inherently occurs during the period required forcomplete hydrolysis. Moreover, it will be readily apparent that the useof elevated temperatures to accelerate hydrolysis of the interpolymerwill exert a like accelerating effect upon the insolubilizationreaction, with the obvious result that the pot-life is severelydiminished. Accordingly, the realization of optimum results is furtherassured by conducting at least a substantial portion of the hydrolysisreaction, e.g., 6575%, in the absence of the glue product.

The interpolymer material may be fully hydrolyzed or partiallyhydrolized as desired. Additionally, the alkyl vinyl ether/maleicanhydride interpolymer may also be partially esterified, the onlycriticality relative to a partial esterification being that a sufficientnumber of carboxylic groups must remain available for cross-linking withthe glue or gelatin material.

Other interpolymer materials which have been found satisfactory for usein forming the binder compositions of this invention include suchmaterials as Acrysol A3, a polyacrylic acid composition sold under thattrade name designated by Rohm and Haas Company, which polymer must besubjected to hydrolysis under the conditions set forth hereinabove. Ofthese interpolymer compositions, however, the Gantrez-an materials soldby General Aniline & Film Corporation represent preferred compositionsfor use in the invention.

The proportions of hydrolyzed interpolymer employed in the presentbinder compositions range from about 1 to about 100 parts per 100 partsof animal or fish glue or gelatin. However, particularly advantageousglue insolubilization systems are obtained with proportions ofhydrolyzed interpolymers ranging from about 5 to about 25 parts per 100parts of glue on a dry-weight basis.

The binder compositions of the present invention may be prepared in anydesired manner and the components added in any desired order.Preferably, however, the

aqueous solution of hydrolyzed or partially hydrolyzed interpolymer isadded to a pre-formed aqueous solution of the animal and/ or fish gluewhich has been heated to its liquefaction temperature. Stirring may beemployed, if desired, to promote inter-dispersion of the respective glueand polymer solutions. At this stage, any other ingredients, such as anaccelerator, filler, etc., desired o be included in the bindercomposition, may be added. The said other ingredients may, of course,also be included in either of the polymer or glue solutions instead ofadding the same separately to the aqueous, hydrolyzed intermixture.

As indicated hereinbefore, the insolubilization of the glue to form thebinders will occur at room temperature although it is advisable from aneconomic standpoint to maintain the composition under an elevatedtemperature, in order to. accelerate gel formation. However, .it shouldbe understood that other means may be employed to ad vantage to effectthe rate of insolubilization, pot-life, and the like.

In this respect, it has been determined that advantageous results areobtained if means are employed to accelerate the degree and rate of theinsolubilization reaction. In particular, it has been discovered,through the use of laboratory experimentation, that the use of thehereinafter enumerated accelerating means or materials serve tosynergistically modify the binder compositions by exerting a catalyticeffect on the rate of insolubilization. Increasing the rate ofinsolubilization has been found to result in a significant increase inthe rub resistance of the striker compositions while simultaneouslyincreasing the pot-life of the compositions.

Several methods are available for acceleration of the insolubilizationprocess in satisfaction of the abovedefined advantages. The foremostmethods comprise the use of higher molecular weight grades of hydrolyzedinterpolymer and the addition of various chemical materials. Of thechemical materials which have been found useful in accelerating theinsolubilization reaction, synthetic organic resin materials whichcontain a plurality of groups reactive towards the glue molecule havebeen found to be particularly benefical. Of the several materialsencompassed by this definition, there may be mentioned the methylatedmethylol melamine resins. Of these several materials, a methylatedmethylol melamine resin sold commercially by the Monsanto ChemicalCompany under the trade name designation Resloom M-75 has been found tobe particularly outstanding as an accelerator. In addition to theseresins, a number of other materials, such as the alkali metalbichromates, (e.g., sodium bichromate, potassium bichromate, etc.),polyamines, polyepoxides, polyisocyanates, etc., have been found to beparticularly suitable accelerator materials for the compositions.

Other accelerating additives which have been found satisfactory for usein the compositions of this invention include such materials as urea,Kymene 557, a cationic, water-soluble resin sold commercially under thatname by Hercules Powder Company, ammonium zirconyl carbonate andVinol-125, a polyvinyl alcohol composition sold commercially by AircoChemical. However, it is to be understood that the use of the alkalimetal bichromates and Resloom M75 as accelerators represent preferredaspects of the invention.

Compositions found to be particularly advantageous in the sense ofproviding improved pot-life and excellent water-resistant propertiescomprise as essential ingredients a hydrolyzed methyl vinyl ether/maleicacid interpolymer with low gel strength bone glue and, as theaccelerator, an alkylated alkylol melamine resin.

The proportions of the accelerator materials employed in formulating theglue compositions are not particularly critical as depending primarilyon the requirements of the processor as Well as the molecular weight ofthe hydrolyzed interpolymer, the type of glue, etc. However, it has beenfound that optimum results are obtained when the above-mentionedmaterials are employed in concentrations ranging from about 0.05 toabout 50 parts per 100 parts of the glue material.

In forming the binder compositions for use in the striker compositionsof the invention, it has been observed that variations in thecomposition ingredients will affect the properties of the resultantproduct and/or the rate at which insolubilization occurs. For example,it has been observed that, as the molecular weight of the hydrolyzedalkyl vinyl ether/maleic anhydride interpolymer increases, the pot-lifeof the glue compositions containing it decreases, whereas the rate anddegree of the insolubilization reaction increases. Moreover, it has beenobserved that the degree and rate of insolubilization of glue containingan identical percentage of the same molecular weight grade of hydrolyzedinterpolymer appears to be greater for high gel strength high glue asopposed to low gel strength bone glue.

As a general proposition, it has been discovered that satisfactorybinder compositions for use in the matchstriker compositions of thisinvention may be represented by the following general formula with partsgiven by weight.

Ingredient: Parts by weight Glue or gelatin 100 Hydrolyzed interpolymer1-100 Accelerator 0.05- 50 The resulting mixture may be brought to thedesired solids content and viscosity by the addition of water and/ or anorganic solvent.

An even more specific and preferred mixture of components would include5-25 parts of the hydrolyzed alkyl vinyl ether/maleic anhydrideinterpolymer and 0.25-12.5 parts of accelerator based on 100 parts ofglue.

The striker compositions of the present invention, as pointed outhereinabove, are formed by admixture of the above-described bindercomposition with a suitable igniting agent and a friction agent.

A generalized match-striker composition according to this invention maybe as follows, the parts being given by weight.

Ingredient: Parts by weight Binder Igniting agent 60 Friction agent Thebinder ingredient is, of course, the composition described in detailhereinabove.

The igniting agents which are employed in the compositions of thisinvention include such well-known materials as red phosphorous, redantimony sulfide, and the like. However, it should be understood thatother igniting agents, such as are commonly used in the match-strikerart, may be included in the compositions of this invention.

A preferred friction agent for use in forming the striker compositionsof this invention is powdered or ground glass which is commonly employedin compositions of this type. However, other friction agents, such assilica sand, for example, which are adapted to provide the necessaryfriction may be employed as desired. A particularly desirable frictionagent is Ground Glass No. 80 sold commercially under that name by TheBassichis Company.

It is to be understood that the striker composition may also containadditional ingredients which are generally well known in the art for theattainment of the required consistency, etc. For example, inertingredients, such as whiting, clay, zinc oxide, and carbon black,viscosity control agents, liquid diluents, dispersing agents, andignitable substances, such as paraflin, gums, rosin, etc., may beemployed as desired in the compositions. Also, other materials, such asinert fillers, coloring pigments, and the like may be added as desired.All of these materials are well known in the art.

Preparation of a match-striker composition according to this inventionmay be carried out generally as follows:

Dried powdered glue of any gel strength, but preferably from 200 to 400grams gel strength (by Bloom Gelometer rating) is stirred into coldwater until the particles are wet and then is allowed to swell. Theswollen glue is then solvated at about 38 to 60 C. (100 to 140 F.) asdescribed above. It should be noted here that direct solution of theglue in hot water is possible but use of this technique often causesentrapment of unwetted glue particles. Therefore, direct stirring of thedried, powered glue into cold water represents a preferred aspect of thematchstriker composition preparation.

To this glue solution maintained at about 38 C. to about 60 C. undermechanical agitation is added the aqueous hydrolyzed solution of thealkyl vinyl ether/ maleic anhydride interpolymer or its partial ester.

It should be noted that low gel strength glue solutions are often liquidat room temperature whereas high solids, high gel strength gluesolutions must necessarily be maintained at about 60 C. to insure theirfluidity. Obviously then, the glue solution should be fluid enough toaccept the addition of the compounding materials.

The addition of the hydrolyzed interpolymer or its partial ester is thenfollowed by the addition of the accelerator material either in dry formor as a liquid dispersion. After addition of the accelerator, theigniting agents and friction agents may be added. Preferably, thesematerials are added to the blend as aqueous slurries as this has beenfound to be the most convenient and satisfactory method of perfectingthe addition of these materials. However, it is also within the scope ofthis inventoin to add these materials by other means, such as by siftingthe solids into the binder mixture.

After the addition of each of the above ingredients, the resultingmixture is in the form of an aqueous slurry and may be applied directlyto the desirable substrate. The preferred substrates for application arethe cellulosic substrates, such as ordinarily used in formingmatch-striker compositions.

The match-striker composition can be applied to the substrates, such aspaper or wood, by any means known to the trade. Such means include theordinary use of such apparatus as transfer rolls, doctor blades, airknives, intaglio printing, and the like.

After application of the aqueous slurry to the substrate, it isnecessary to effect curing of the coated composition in view of the factthat the applied film generally contains water and/or organic solvents,depending on the solvent employed, which are necessary to be evaporated.Although these volatiles will evaporate from the coating at roomtemperature, this method is too slow for use in mass productiontechniques. It has, therefore, been found that evaporation of thevolatiles and cure of the coating can be effected in one step bysubjecting the coated substrate to an elevated temperature. According toa preferred embodiment of this invention, a drying temperature of fromabout 50 C. to about C., preferably about 60 C., has been found to beparticularly suitable to effect the curing and drying steps wheresuitable equipment is employed. Such equipment may include circulatinghotair ovens, infra-red heaters, high-frequency heating coils, and thelike. The only limitations to be encountered in carrying out theseheating and curing steps is to insure that combustion does not occur. Ithas been found that coatings which are cured for about 3 minutes at 60C. and then aged at room temperature for about hours are quite waterresistant and, therfore, the use of this curing technique represents apreferred aspect of the present invention.

The compositions of the following examples are given for the purpose ofillustrating various embodiments of the present invention and are not tobe regarded in any Way as being limitative thereof. All parts are givenby weight on wet basis and solid concentrations are as indicated.

Representative glue stocks were initially prepared for use as binders bysolvating animal (hide) glue in distilled water containing apreservative (phenol) at 60 C. according to the following formula withparts being by weight.

Ingredient: Parts by weight Cold distilled water 49.5 Phenol 0.5 Animal(hide) glue 50.0

for the various periods set forth in the following table. Thereafter,the applied striker composition was dried at 60 C. for 3 minutes and thecard containing it immersed in tap water for 2 minutes. Then, afterremoving from the water, a Kleenex tissue was rubbed across the stillwet card. The tissue should not pick up any of the red phosphorous fromthe applied composition.

The results of this test, which demonstrates both rub resistance andresistance to water, are set forth in the tabular form in Table Ihereinbelow. In the tests, the degree of red phosphorous pick-up wasrated as from minusone (l) to plus-seven (+7). Minus-one (1) indicatedno pick-up whereas plus-seven (+7) indicated the heaviest pick-up.

RUB RESISTANCE OF STRIKER COMPOSITIONS 30 Min. at 3 Min. at 3 Min. at 3Min. at 60 C. 2 3 Min. at 30 Min. at 60 C. 24 60 C. 100 60 C. 2 months a60 C. 60 C. hrs. at RT. hrs. at RT. \vks.at RT. RT

(1) 379 g. Hide Glue, 10% Hyd. Gantrez AN-119 6 2 (2) 379 g. Hide Glue,20% Hyd. Gantrez AN-1l9. 7 4 (3) 120 g. Bone Glue, 20% Hyd. GantrezAN-l19.. 7 6 (4) 379 g. Hide Glue, 20% Acrysol A-3 7 +4 to 6 (5) 379 g.Hide Glue, 20% Hyd. Gantrez AN-119, 5% Urea r. 7 5 (6) 379 g. Hide Glue,20% Hyd. Gantrez AN-119, 5% Kymene 557,. 6 +3 (7) 379 g. Hide Glue, 20%Hyd. Gantrez AN-1l9, 25% Kymene 557. 7 (8) 379 g. Hide Glue, 20% Hyd.Gantrez AN-llt), 5% Ammonium Zirconyl Carbonate. 7 6 (9) 379 g. HideGlue,

B ichromate 7 +3 (10) 379 g. Hide Glue, 20% Hyd. Gantrez AN-139, 10%Vinol 125. 7 4 (11) 379 g. Hide Glue, 20% Hyd. Gantrez AN-139 7 3 to 4(12) 379 g. Hide Glue, Hyd. Gantrez ANY-139, 5% Acrysol A3 7 (13A) 379g. Hide Glue, 10% Hyd. Gantrez AN-139, 10% Acrysol 7 5 (14) 379 g. HideGlue, Hyd. Gantrez AN-139, 5% Resloorn M- 7 +1 07 2 t07 1 to +1 -1t01 +1to -2 (15) 379 g. Hide Glue, Hyd. Gantrez AN-139, 5% Resloom M-75 6 3 +11 1 to +1 (ltliv)I 1;;9 g. Hide Glue, 20% Hyd. Gantrez AN-l 50% Resloom6 1 1 1 (17) 379 g e ue, 10% Hyd. G a Rcsloom 75 7 4 4 4 +2 (18) 379 ge, 10% Dry Resloorn M-75 on Dry Weight of Glue Gelled immediately In allcases hydrolyzed Gantrez AN percent is the percent dry weight based onthe dry weight of glue, the same being true for the Acrysol .A-3

and Vinol.

Percent of urea, Kymene 557, Ammonium Zireonyl Carbonate, SodiumBichromate, and Resloom M-75 are their percent dry weight based on thedry weight of Hyd. Gantrez An. Kymene 557-Cationic, water soluble resinfrom Hercules Powder Company. Aerysol A-3-Polyacrylic acid irom Rohm andHaas. Vinol 125P0lyvinyl alcohol from Aireo Chemical. ResloomM75-Methylated methylol melamine resin from Monsanto Chemical Company.

Rub Resistance Ratings: Excellent to Poor, 1 to +7.

Material Parts by weight Red phosphorous 29.75 Ground Glass No. 80 12.75Cold distilled water 42.50

The basic striker formula set forth hereinabove was employed in formingstriker compositions for testing which includes 15 parts by weight ofbinder, 60 parts by weight igniting agent and 25 parts by weightfriction agent.

After preparation of each of the required starting compositions, thestriker compositions were prepared employing this basic formula. To theaqueous glue binders maintained at 60 C. with agitation, was added theappropriate amount of striker slurry which had been preheated to 60 C.

After formation of the several representative striker compositions, asdelineated in the following table, they were subjected to a standardtest to determine their rub resistance as follows:

By means of a glass rod, buttons of each striker composition lwereapplied to cigarette carton kraft and cured It is to be noted from theresults of the rub resistance test set forth in the above examples thatparticularly advantageous and desirable match-striker compositions areobtained where the compositions are accelerator cured. See, forinstance, Examples 9 and 13-16.

It is also to be noted from the above results that Examples 1 and 2 showthe difference in performance of the compositions as a function of thehydrolyzed polyvinyl methyl/rnaleic anhydride interpolymerconcentration, whereas Examples 2 and 3 show the difference inperformance of the compositions as a function of glue gel rating.

It should be understood that various other ingredients may be includedin the compositions provided by the present invention in addition tothose specifically enumerated hereinbefore. For example, the physicalcharacteristics of the interpolymer-glue blend may be modified in degreeby the incorporation of various compatible materials as desired in orderto modify or adjust the physical or other characteristics of a givenformula. As examples of such ingredients, there may be mentionedplasticizers, humectants, diluents, fillers, and the like.

The invention has been disclosed with respect to certain preferredembodiments thereof, and there will become obvious to persons skilled inthe art various modifications, equivalents or variations thereof whichare intended to be included within the spirit and scope of theinvention.

What is claimed is:

1. A water-proof match-striker composition comprising an igniting agent,a friction agent, and a water-dispersed binder material to cement theigniting agent and friction agent into a coherent mass, the bindermaterial comprising (1) a proteinaceous adhesive material and (2) ahydrolyzed interpolymer of an alkyl vinyl ether and maleic anhydride,said proteinaceous adhesive material and said hydrolyzed interpolymerbeing cross-linked by heat to a water-insoluble state.

2. A match-striker composition according to claim 1 wherein theproteinaceous material is selected from the group consisting of animalglue, fish glue, and gelatin.

3. A match-striker composition according to claim 1 wherein the alkylvinyl ether comprises methyl vinyl ether.

4. A match-striker composition according to claim 1 which furthercontains a compound which accelerates insolubilization of the saidbinder material.

5. A match-striker composition according to claim 4 wherein theaccelerator material is selected from the group consisting of (1) analkylated alkylol melamine resin containing a plurality of pendantalkylol groups and (2) an alkali metal bichromate.

6. A match-striker composition according to claim 5 wherein theaccelerator material comprises methylated methylol melamine resins.

7. A match-striker composition according to claim 1 which comprises 1 to100 parts of hydrolyzed interpolymer of an alkyl vinyl ether and maleicanhydride per 100 parts of proteinaceous material on a dry basis andfrom .05 to parts of accelerator material per parts of proteinaceousmaterial.

8. A composition according to claim 7 wherein the proteinaceous materialis selected from the group consisting of animal glue, fish glue andgelatin.

9. A composition according to claim 8 wherein the alkyl vinyl ethercomprises methyl vinyl ether.

10. A match-striker composition according to claim 9 wherein theaccelerator material is selected from the group consisting of analkylated alkylol melamine resin containing a plurality of dependentalkylol groups and an alkali metal dichromate.

References Cited UNITED STATES PATENTS 660,366 10/1900 Craveri 44482,589,607 3/1952 Ellern 44-48 X 2,683,098 7/1954 Sinks 44-48 X 3,202,5398/1965 Holt et al 260- 8 X 3,313,749 4/1967 Ready 260-8 DANIEL F.WYMA-N, Primary Examiner. C. F. DEES, Assistant Examiner.

US. 01. X.R. 44 4s

